Underwater antifouling paint and preparation method thereof

Abstract

The present invention relates to the field of coatings, and in particular to an underwater antifouling paint and a preparation method thereof. The underwater antifouling paint comprises 2-5 parts of chlorinated rubber, 1-3 parts of chloroether resin, 1-2 parts of zinc acrylate resin, 35-50 parts of antifouling agent, 9-12 parts of compounded rosin, 2-5 parts of toughening agent, 1-3 parts of stabilizer, 2-5 parts of defoaming agent, 0.1-0.5 parts of dispersant, 2-3 parts of thixotropic agent, and 15-25 parts of solvent; the antifouling agent comprises cuprous oxide, an organic antifouling agent, and a natural biological antifouling agent; the compounded rosin comprises gum rosin and rosin maleic anhydride polyol ester; the toughening agent comprises sorbitan fatty acid ester and tricresyl phosphate; and the stabilizer comprises zinc oxide and polyoxyethylene fatty alcohol ether. The underwater antifouling paint of the present invention has high adhesion, flexibility, impact resistance, water resistance, and excellent antifouling performance, and is suitable for ship bottoms and underwater facilities.

Description

Technical Field

[0001] The present invention relates to the field of coatings, and in particular to an underwater antifouling paint and a preparation method thereof. Background Art

[0002] In underwater antifouling paints, the release rate and uniformity of the antifouling agent are critical. If the antifouling agent is released too quickly, the antifouling cycle will be shortened, while uneven release may result in poor localized antifouling effectiveness. Traditional chlorinated rubber antifouling paints are dissolving-type antifouling paints made with chlorinated rubber as the backbone, rosin as the slow-release agent, and antifouling agents such as cuprous oxide. As the rosin resin continuously dissolves in water, the paint film is constantly renewed, and the contained antifouling agent is continuously released to exert its antifouling effect. However, due to the excessive amount of chlorinated rubber, the paint film forms a saponification layer, which continuously reduces the antifouling agent's seepage rate and even causes the copper ions to form insoluble salts such as basic copper carbonate, further reducing the seepage rate until the antifouling coating fails.

[0003] In addition, due to the poor mechanical properties of traditional chlorinated rubber antifouling paint, such as adhesion, flexibility and stability, the paint film cannot effectively resist the scouring and erosion of water flow. Therefore, the chlorinated rubber antifouling paint currently used generally has the problem of short lifespan. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the deficiencies and defects in the prior art, thereby providing an underwater antifouling paint with high paint film flexibility and stability and strong adhesion, and a preparation method thereof.

[0005] To solve the above problems:

[0006] The present invention provides an underwater antifouling paint comprising the following components in parts by weight:

[0007] 2-5 parts of chlorinated rubber, 1-3 parts of chloroether resin, 1-2 parts of zinc acrylate resin, 35-50 parts of antifouling agent, 9-12 parts of compound rosin, 2-5 parts of toughening agent, 1-3 parts of stabilizer, 2-5 parts of defoaming agent, 0.1-0.5 parts of dispersant, 2-3 parts of thixotropic agent, 15-25 parts of solvent;

[0008] The antifouling agents include cuprous oxide, organic antifouling agents and natural biological antifouling agents;

[0009] The compound rosin includes gum rosin and rosin maleic anhydride polyol ester;

[0010] The toughening agent includes sorbitan fatty acid ester and tricresyl phosphate;

[0011] The stabilizer includes zinc oxide and polyoxyethylene fatty alcohol ether.

[0012] In the present invention, a single chlorinated rubber is used as the film-forming substance of the antifouling paint, which gives the paint film certain adhesion and quick-drying properties. However, the flexibility of this paint film is relatively poor, and it is easy to form a saponification layer that continuously reduces the permeability of the antifouling agent. The use of a single zinc acrylate resin as the film-forming substance can prevent marine organisms from adhering to the hull and underwater facilities, and the pollution to the marine environment is relatively small. However, the viscosity of the zinc acrylate resin is large, the paint film takes a long time to dry, affecting the construction efficiency, and the paint film has poor corrosion resistance. The present invention uses a compound of chlorinated rubber, chloroether resin and zinc acrylate resin as the main carrier of the antifouling paint. The three are intertwined to form a slow-release channel for the antifouling agent and a relatively stable physical barrier, which regulates the diffusion rate of the antifouling agent while preventing the loss of the antifouling agent when not in use. In addition, during use, the antifouling agent wrapped inside the paint film is gradually exposed and released through the continuous renewal of the paint film surface, thereby achieving a stable antifouling effect over a long period of time and extending the antifouling life.

[0013] In the present invention, cuprous oxide is an antifouling agent widely used in antifouling paints. It slowly dissolves in water and releases copper ions to form a toxic water layer on the paint film surface, which has the ability to kill bacteria, remove algae, and prevent biological adhesion. However, the unstable copper ion leakage rate can affect the antifouling effect and lifespan of the coating. By introducing an organic antifouling agent, a natural biological antifouling agent, and a composite of cuprous oxide, the organic antifouling agent and the natural biological antifouling agent are filled between the cuprous oxide particles to form a slow-release carrier. The release rates are coordinated with each other, thereby improving the broad-spectrum bactericidal and antibacterial capabilities of the antifouling paint, effectively preventing the growth and adhesion of various microorganisms on the surface of the antifouling paint, and enhancing the antifouling performance of the paint. The cuprous oxide release is slower and more lasting, ensuring the stable antifouling effect of the antifouling agent and extending the service life of the antifouling paint.

[0014] In the present invention, the compounded rosin is a compound of gum rosin and rosin maleic anhydride polyol ester. The slight solubility of gum rosin in seawater is conducive to the release of antifouling agents, but when gum rosin is used as a coating matrix, there are problems such as too fast release rate and insufficient mechanical properties of the coating. The compounded rosin in the present invention is a compound of gum rosin and rosin maleic anhydride polyol ester. Rosin maleic anhydride polyol ester has structural characteristics including ester groups, carboxyl groups, hydroxyl groups, and multiple cyclic structures. It can adjust the microstructure and porosity of the antifouling paint, form a relatively stable permeation layer in seawater, control the dissolution rate of gum rosin, thereby slowing down the release rate of the antifouling agent, allowing the antifouling agent to be released more evenly within the service life of the coating, thereby achieving a better antifouling effect.

[0015] In the present invention, tricresyl phosphate acts as a toughening agent and can be inserted between polymer molecular chains to improve the flexibility of the paint film. However, in antifouling paints, excessive use of tricresyl phosphate can affect the permeability of the paint film and hinder the release of the antifouling agent. By introducing sorbitan fatty acid esters and compounding them with tricresyl phosphate, the uniform dispersion of tricresyl phosphate in the antifouling paint is promoted, and the wetting and spreading of the paint film on the substrate surface are promoted, thereby reducing the internal stress of the antifouling paint and further improving the flexibility and impact resistance of the antifouling paint. This makes the paint film less likely to crack or peel when subjected to external forces, avoids sedimentation and delamination of the antifouling agent, improves the uniformity, stability and density of the paint film, and enhances the flatness and water resistance of the paint film. The introduction of sorbitan fatty acid esters controls the distribution and migration speed of the antifouling agent in the paint film, thereby regulating the release rate of the antifouling agent, and enabling the antifouling paint to maintain a stable antifouling effect over a long period of time.

[0016] In the present invention, zinc oxide, as a stabilizer, can improve the hardness and antifouling performance of antifouling paints. However, zinc oxide easily agglomerates, resulting in uneven dispersion within the coating, thus affecting the performance of the paint film. In the present invention, polyoxyethylene fatty alcohol ether is compounded with zinc oxide and then coated on the surface of zinc oxide particles, reducing the surface energy of the zinc oxide particles. This avoids the phenomenon of uneven zinc oxide dispersion leading to unstable performance in localized areas, making the resulting paint film more uniform and dense, and improving the hardness and toughness of the paint film. The compounded stabilizer is not only less toxic and can reduce the environmental pollution of the antifouling paint, but also regulates the release of the antifouling agent from the antifouling paint by improving the chemical stability of the antifouling paint and adjusting the pore structure and diffusion properties of the paint film.

[0017] Preferably, the organic antifouling agent includes copper pyridinethione and / or 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one; and the natural biological antifouling agent includes one or more of capsaicin, gingerol and chitosan.

[0018] Preferably, the mass ratio of the cuprous oxide, the organic antifouling agent and the natural biological antifouling agent is (8-15): (1-2): (1-3); the mass ratio of the gum rosin and the rosin maleic anhydride polyol ester is (2-5): 1; the mass ratio of the sorbitan fatty acid ester and tricresyl phosphate is 1: (3-9); and the mass ratio of the zinc oxide and the polyoxyethylene fatty alcohol ether is (4-9): 1.

[0019] In the present invention, in order to ensure the antifouling effect while reducing the usage of cuprous oxide and further reduce the negative impact on the marine ecological environment, the mass ratio of cuprous oxide, organic antifouling agent and natural biological antifouling agent is (8-15): (1-2): (1-3).

[0020] In the present invention, a higher mass ratio of gum rosin to rosin maleic anhydride polyol ester reduces the paint film's flexibility and increases its brittleness, making it susceptible to cracking when subjected to external forces, thus affecting its antifouling effectiveness. A lower mass ratio of gum rosin to rosin maleic anhydride polyol ester improves the film's water resistance, flexibility, and impact resistance, but also slows its dissolution rate, hindering the release of the antifouling agent and also affecting its antifouling effectiveness. An appropriate blending ratio can enhance the film's adhesion, balance its hardness and toughness, improve its antifouling effectiveness, and extend its service life. Therefore, the mass ratio of gum rosin to rosin maleic anhydride polyol ester is (2-5):1.

[0021] In the present invention, in order to improve the flexibility of the paint film and avoid the influence of the toughening agent on the antifouling performance, thereby ensuring that the antifouling paint maintains a stable antifouling effect over a long period of time, the mass ratio of the sorbitan fatty acid ester to tricresyl phosphate is 1:(3-9).

[0022] In the present invention, in order to better improve the performance of the antifouling paint and reduce environmental pollution, the mass ratio of zinc oxide to polyoxyethylene fatty alcohol ether is (4-9):1.

[0023] Preferably, the sorbitan fatty acid ester includes one or more of Span-60, Span-80 and Span-85; and the polyoxyethylene fatty alcohol ether is selected from one or more of AEO-9, MOA-9 and Parvalbumin O.

[0024] Preferably, the chlorinated rubber is selected from one or more of S-20, CRF20 and CR-20; the chloroether resin is MP-45; and the zinc acrylate resin is SPZn-100 and / or H100Z.

[0025] In the present invention, in order to control the release rate of the antifouling agent, improve the antifouling effect, ensure the smoothness of the coating surface, and improve the water resistance and adhesion of the coating, the zinc acrylate resin is SPZn-100 and / or H100Z.

[0026] Preferably, the chlorine content in the chlorinated rubber is 64-68%, and the chlorine content in the chloroether resin is 42-46%.

[0027] In the present invention, the higher the chlorine content of the chlorinated rubber and the chloroether resin, the better the antifouling effect, hardness and water resistance of the coating. However, an excessively high chlorine content increases the rigidity of the molecular chain, reduces the flexibility and impact resistance of the coating, and affects the marine environment. The lower the chlorine content of the chlorinated rubber and the chloroether resin, the better the flexibility, but the slower the drying speed and the worse the antifouling effect. Therefore, the chlorine content of the chlorinated rubber is 64-68%, and the chlorine content of the chloroether resin is 42-46%.

[0028] Preferably, the defoaming agent is a fluorine-free resin defoaming agent, and the fluorine-free resin defoaming agent is one or more of BYK-052, Tego-810, HY-5300 and TEGO Foamex 825; the dispersant is one or more of BYK-190, EFKA-4010 and SN-5027; the thixotropic agent is one or more of organic bentonite, polyamide wax, fumed silica, and hydrogenated castor oil; and the solvent is one or more of xylene, 100# gasoline, butyl acetate, n-butanol, methyl ethyl ketone, isopropyl alcohol, and butyl acetate.

[0029] The present invention also provides a method for preparing the underwater antifouling paint, comprising the following steps:

[0030] (1) Mixing and stirring the solvent, chlorinated rubber, chloroether resin, zinc acrylate resin, and compounded rosin to obtain a first mixture;

[0031] (2) adding a thixotropic agent, a dispersant, a defoaming agent, and a toughening agent to the first mixture, mixing and stirring to obtain a second mixture;

[0032] (3) adding an antifouling agent and a stabilizer to the second mixture, mixing and stirring to obtain a third mixture, adding a solvent to the third mixture, mixing evenly, and filtering to obtain the underwater antifouling paint.

[0033] Preferably, the mixing and stirring speed in step (1) is 1000-1500 r / min; the fineness of the third mixture in step (3) is less than 40 μm, and the viscosity of the third mixture after adding the solvent is 100-120 KU.

[0034] Preferably, the mixing and stirring time in step (1) is 20 minutes; and the mixing and stirring time in step (2) is 30-40 minutes.

[0035] The technical solution of the present invention has the following advantages:

[0036] 1. The underwater antifouling paint provided by the present invention overcomes the adverse effects of using only chlorinated rubber or only zinc acrylate resin as film-forming substances, and enhances the chemical stability and physical properties of the paint film through synergistic effects. In addition, by compounding cuprous oxide with organic antifouling agents and natural biological antifouling agents, the antifouling performance is improved, and a stable antifouling effect can be maintained for a long time, thereby extending the antifouling life. In addition, the paint film properties of the antifouling paint are improved, the flexibility, adhesion and water resistance of the paint film are enhanced, and the durability of the antifouling paint is improved, so that the paint film can better resist the scouring and erosion of water flow. When the paint film is subjected to impact or expands and contracts due to temperature changes, it can remain intact without cracking.

[0037] 2. The underwater antifouling paint provided by the present invention uses a compound of gum rosin and rosin maleic anhydride polyol ester, which not only can better control the release rate of the antifouling agent, but also enhances the adhesion between the antifouling paint and the substrate, improves the leveling performance of the antifouling paint, makes the paint film surface smoother, and can form a balance of hardness and toughness in the paint film, so that the paint film can resist the erosion of water flow and the scratching of aquatic organisms, while avoiding brittle cracking due to excessive hardness, thereby extending the service life of the paint film.

[0038] 3. The underwater antifouling paint provided by the present invention incorporates a compound of sorbitan fatty acid ester and tricresyl phosphate as a toughening agent, promoting the uniform dispersion of tricresyl phosphate in the antifouling paint and promoting the wetting and spreading of the paint film on the substrate surface, thereby reducing the internal stress of the antifouling paint, enhancing the flexibility of the paint film, and improving the impact resistance and crack resistance of the paint film. The introduction of sorbitan fatty acid ester effectively prevents sedimentation and stratification of the antifouling paint, improving the uniformity, stability, and density of the paint film. Furthermore, by forming a hydrophobic layer, it prevents water penetration and erosion, thereby improving the water resistance of the paint film and preventing the paint film from swelling, softening, and blistering due to long-term contact with seawater.

[0039] 4. The underwater antifouling paint provided by the present invention uses a polyoxyethylene fatty alcohol ether and zinc oxide as a stabilizer, avoiding the phenomenon of uneven zinc oxide dispersion leading to unstable performance in local areas, making the formed paint film more uniform and dense, improving the hardness and toughness of the paint film, and allowing the antifouling agent to be released slowly and evenly over a long period of time. The introduction of polyoxyethylene fatty alcohol ether also improves the cohesion of the paint layer through interaction with other ingredients, strengthens the adhesion between the paint film and the substrate, and extends the antifouling period. DETAILED DESCRIPTION

[0040] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0041] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents. Example 1

[0042] The present invention provides an underwater antifouling paint comprising the following components in parts by weight:

[0043] 2 parts of chlorinated rubber S-20, 3 parts of chlorinated rubber CRF20, 3 parts of chloroether resin MP-45, 1 part of zinc acrylate resin SPZn-100, 1 part of zinc acrylate resin H100Z, 30 parts of cuprous oxide, 2 parts of copper pyridinethione (organic antifouling agent), 2 parts of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (organic antifouling agent), 3 parts of capsaicin (natural bio-antifouling agent), 3 parts of gingerol (natural bio-antifouling agent), 10 parts of gum rosin, 2 parts of rosin maleic anhydride polyol Alcohol ester, 0.2 parts of Span-80 (toughener), 0.3 parts of Span-60 (toughener), 4.5 parts of tricresyl phosphate (toughener), 2.7 parts of zinc oxide (stabilizer), 0.3 parts of AEO-9 (stabilizer), 5 parts of BYK-052 (defoaming agent), 0.2 parts of BYK-190 (dispersant), 0.3 parts of EFKA-4010 (dispersant), 3 parts of organic bentonite (thixotropic agent), 10 parts of ethyl acetate (solvent), 10 parts of n-butanol (solvent).

[0044] The preparation method of the underwater antifouling paint comprises:

[0045] (1) Add 10 parts of ethyl acetate (solvent) into a dispersion kettle, stir and add 2 parts of S-20 (chlorinated rubber), 3 parts of CRF20 (chlorinated rubber), 3 parts of MP-45 (chloroether resin), 1 part of SPZn-100 (zinc acrylate resin) and 1 part of H100Z (zinc acrylate resin), and then add 10 parts of gum rosin and 2 parts of rosin maleic anhydride polyol ester (compounded rosin) dissolved in 5 parts of n-butanol in advance, adjust the speed to 1500r / min, and disperse for 20 minutes to obtain the first mixture;

[0046] (2) Add 3 parts of organic bentonite (thixotropic agent), 0.2 parts of BYK-190 (dispersant), 0.3 parts of EFKA-4010 (dispersant), 5 parts of BYK-052 (defoaming agent), 0.2 parts of Span-80 (toughening agent), 0.3 parts of Span-60 (toughening agent), and 4.5 parts of tricresol phosphate (toughening agent) to the first mixture, and continue stirring for 40 minutes until the mixture is uniform to obtain the second mixture;

[0047] (3) Add 30 parts of cuprous oxide (antifouling agent), 2 parts of copper pyridinethione (organic antifouling agent), 2 parts of 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of capsaicin (natural biological antifouling agent), 3 parts of gingerol (natural biological antifouling agent), 2.7 parts of zinc oxide (stabilizer), and 0.3 parts of AEO-9 (stabilizer) to the second mixture, and stir until the fineness is less than 40 μm to form a slurry, that is, to obtain a third mixture. Add 5 parts of n-butanol (solvent) to the third mixture to adjust the viscosity to 100-120 KU, and filter to obtain the underwater antifouling paint. Example 2

[0048] The present invention provides an underwater antifouling paint comprising the following components in parts by weight:

[0049] 4 parts of chlorinated rubber CR-20, 2 parts of chloroether resin MP-45, 1 part of zinc acrylate resin H100Z, 40 parts of cuprous oxide, 5 parts of copper pyridinethione (organic antifouling agent), 5 parts of capsaicin (natural biological antifouling agent), 8 parts of gum rosin, 2 parts of rosin maleic anhydride polyol ester, 1 part of Span-80 (toughening agent), 3 parts of tricresyl phosphate (toughening agent), 2.5 parts of zinc oxide (stabilizer), 0.5 parts of MOA-9 (stabilizer), 2 parts of Tego-810 (defoaming agent), 0.3 parts of EFKA-4010 (dispersing agent), 2 parts of polyamide wax (thixotropic agent), 25 parts of xylene (solvent).

[0050] The preparation method of the underwater antifouling paint comprises:

[0051] (1) Add 10 parts of xylene (solvent) into a dispersion kettle, stir and add 4 parts of CR-20 (chlorinated rubber), 2 parts of MP-45 (chloroether resin), and 1 part of H100Z (zinc acrylate resin), and then add 8 parts of gum rosin and 2 parts of rosin maleic anhydride polyol ester (compounded rosin) dissolved in 10 parts of xylene in advance, adjust the speed to 1000 r / min, and disperse for 20 minutes to obtain the first mixture;

[0052] (2) Add 2 parts of polyamide wax (thixotropic agent), 0.3 parts of EFKA-4010 (dispersant), 2 parts of Tego-810 (defoaming agent), 1 part of Span-80 (toughening agent), and 3 parts of tricresol phosphate (toughening agent) to the first mixture, and continue stirring for 30 minutes until the mixture is uniform to obtain a second mixture;

[0053] (3) Add 40 parts of cuprous oxide (antifouling agent), 5 parts of copper pyrithione (organic antifouling agent), 5 parts of capsaicin (natural biological antifouling agent), 2.5 parts of zinc oxide (stabilizer), and 0.5 parts of MOA-9 (stabilizer) to the second mixture, and stir until the fineness is less than 40 μm to form a slurry, that is, to obtain a third mixture. Add 5 parts of xylene (solvent) to the third mixture to adjust the viscosity to 100-120 KU, and filter to obtain the underwater antifouling paint. Example 3

[0054] The present invention provides an underwater antifouling paint comprising the following components in parts by weight:

[0055] 2 parts of chlorinated rubber CRF20, 1 part of chloroether resin MP-45, 1 part of zinc acrylate resin H100Z, 30 parts of cuprous oxide, 2 parts of 4,5-dichloro-2-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of chitosan (natural biological antifouling agent), 6 parts of gum rosin, 3 parts of rosin maleic anhydride polyol ester, 0.4 parts of Span-85 (toughening agent), 1.6 parts of tricresol phosphate (toughening agent), 0.8 parts of zinc oxide (stabilizer), 0.1 parts of peregal O (stabilizer), 0.1 parts of AEO-9 (stabilizer), 2 parts of HY-5300 (defoaming agent), 2 parts of TEGO Foamex 825 (defoaming agent), 0.1 parts of SN-5027 (dispersant), 2 parts of fumed silica (thixotropic agent), and 15 parts of methyl ethyl ketone (solvent).

[0056] The preparation method of the underwater antifouling paint comprises:

[0057] (1) Add 5 parts of methyl ethyl ketone (solvent) into a dispersion kettle, stir and add 2 parts of CRF20 (chlorinated rubber), 1 part of MP-45 (chloroether resin), and 1 part of H100Z (zinc acrylate resin), and then add 6 parts of gum rosin and 3 parts of rosin maleic anhydride polyol ester (compounded rosin) dissolved in 5 parts of methyl ethyl ketone in advance, adjust the speed to 1300 r / min, and disperse for 20 minutes to obtain the first mixture;

[0058] (2) Add 2 parts of fumed silica (thixotropic agent), 0.1 parts of SN-5027 (dispersant), 2 parts of HY-5300 (defoaming agent), 2 parts of TEGO Foamex 825 (defoaming agent), 0.4 parts of Span-85 (toughening agent), and 1.6 parts of tricresol phosphate (toughening agent) to the first mixture, and continue stirring for 35 minutes until the mixture is uniform, to obtain a second mixture;

[0059] (3) Add 30 parts of cuprous oxide (antifouling agent), 2 parts of 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of chitosan (natural biological antifouling agent), 0.8 parts of zinc oxide (stabilizer), 0.1 parts of peregal O (stabilizer), and 0.1 parts of AEO-9 (stabilizer) to the second mixture, and stir until the fineness is less than 40 μm to form a slurry, thereby obtaining a third mixture. Add 5 parts of methyl ethyl ketone (solvent) to the third mixture to adjust the viscosity to 100-120 KU, and filter to obtain the underwater antifouling paint.

[0060] Comparative Example 1

[0061] This comparative example provides an underwater antifouling paint. The difference from Example 2 is that in this comparative example, the chlorinated rubber CR-20 and the chloroether resin MP-45 are replaced with equal amounts of zinc acrylate resin H100Z, and the organic antifouling agent copper pyridinethione and the natural bioantifouling agent capsaicin are replaced with equal amounts of cuprous oxide.

[0062] Comparative Example 2

[0063] This comparative example provides an underwater antifouling paint. The difference from Example 2 is that this comparative example replaces rosin maleic anhydride polyol ester with an equal amount of gum rosin.

[0064] Comparative Example 3

[0065] This comparative example provides an underwater antifouling paint. The difference from Example 2 is that this comparative example replaces sorbitan fatty acid ester Span-80 with an equal amount of tricresyl phosphate.

[0066] Comparative Example 4

[0067] This comparative example provides an underwater antifouling paint. The difference from Example 2 is that this comparative example replaces polyoxyethylene fatty alcohol ether MOA-9 with an equal amount of zinc oxide.

[0068] In the present invention, the performance of the underwater antifouling paints prepared in Examples 1-3 and Comparative Examples 1-4 was tested according to the performance indicators in Table 1, and the test results are shown in Table 1.

[0069] Table 1 Performance test indicators of coatings and underwater antifouling paint performance test results

[0070]

[0071] As can be seen from Table 1, the underwater antifouling paints provided by the present invention have excellent antifouling performance, antifouling life, adhesion, flexibility, impact resistance and water resistance, and are suitable for ship bottoms and marine underwater facilities.

[0072] Comparison of Comparative Example 1 and Example 2 reveals that the use of a single zinc acrylate resin and a single antifouling agent, cuprous oxide, not only results in limited antifouling effect but also poor mechanical properties of the paint film. The use of a composite film-forming substance and a composite antifouling agent improves the antifouling performance and antifouling life, reduces the drying time of the antifouling paint, and provides an antifouling coating with outstanding flexibility, water resistance, impact resistance, and adhesion.

[0073] By comparing Comparative Example 2 with Example 2, it is found that the introduction of rosin maleic anhydride polyol ester and gum rosin enhances the antifouling performance of the antifouling paint, improves the antifouling effect, and is conducive to enhancing the adhesion between the antifouling paint and the substrate, and improving the impact resistance and other properties of the paint film.

[0074] Comparison of Comparative Example 3 and Example 2 shows that the introduction of sorbitan fatty acid ester and tricresyl phosphate compound not only enhances the flexibility of the paint film, improves the impact resistance of the paint film, and improves the water resistance, but also significantly improves the storage stability of the antifouling paint.

[0075] By comparing Comparative Example 4 and Example 2, it was found that the use of a stabilizer compounded with polyoxyethylene fatty alcohol ether and zinc oxide improved the flexibility of the paint film, enhanced the adhesion between the paint film and the substrate, improved the water resistance of the paint film, and improved the anti-fouling performance.

[0076] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An underwater antifouling paint, characterized in that: The following components are included by weight: 2-5 parts of chlorinated rubber, 1-3 parts of chloroether resin, 1-2 parts of zinc acrylate resin, 35-50 parts of antifouling agent, 9-12 parts of compound rosin, 2-5 parts of toughening agent, 1-3 parts of stabilizer, 2-5 parts of defoaming agent, 0.1-0.5 parts of dispersant, 2-3 parts of thixotropic agent, 15-25 parts of solvent; The antifouling agent comprises cuprous oxide, an organic antifouling agent and a natural biological antifouling agent; the mass ratio of the cuprous oxide, the organic antifouling agent and the natural biological antifouling agent is (8-15): (1-2): (1-3); The natural biofouling agent includes one or more of capsaicin, gingerol and chitosan; The compound rosin comprises gum rosin and rosin maleic anhydride polyol ester; the mass ratio of the gum rosin and rosin maleic anhydride polyol ester is (2-5):1; The toughening agent includes sorbitan fatty acid ester and tricresyl phosphate; the mass ratio of sorbitan fatty acid ester to tricresyl phosphate is 1:(3-9); The stabilizer includes zinc oxide and polyoxyethylene fatty alcohol ether; the mass ratio of zinc oxide to polyoxyethylene fatty alcohol ether is (4-9):

1.

2. An underwater antifouling paint according to claim 1, characterized in that: The organic antifouling agent includes copper pyridinethione and / or 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

3. An underwater antifouling paint according to claim 1, characterized in that: The sorbitan fatty acid ester includes one or more of Span-60, Span-80 and Span-85; The polyoxyethylene fatty alcohol ether is peregal O.

4. The underwater antifouling paint according to claim 1, characterized in that: The chlorinated rubber is selected from one or more of S-20, CRF20 and CR-20; The chloroether resin is MP-45; The zinc acrylate resin is SPZn-100 and / or H100Z.

5. An underwater antifouling paint according to claim 4, characterized in that: The chlorine content of the chlorinated rubber is 64-68%, and the chlorine content of the chloroether resin is 42-46%.

6. The underwater antifouling paint according to claim 1, characterized in that: The defoaming agent is a fluorine-free resin defoaming agent, and the fluorine-free resin defoaming agent is one or more of BYK-052, Tego-810, HY-5300 and TEGO Foamex 825; The dispersant is one or more of BYK-190, EFKA-4010 and SN-5027; The thixotropic agent is one or more of organic bentonite, polyamide wax, fumed silica, and hydrogenated castor oil; The solvent is one or more of xylene, 100# gasoline, butyl acetate, n-butanol, methyl ethyl ketone, isopropyl alcohol, and butyl acetate.

7. The method for preparing the underwater antifouling paint according to any one of claims 1 to 6, characterized in that: The method comprises the following preparation steps: (1) Mixing and stirring the solvent, chlorinated rubber, chloroether resin, zinc acrylate resin, and compounded rosin to obtain a first mixture; (2) adding a thixotropic agent, a dispersant, a defoaming agent, and a toughening agent to the first mixture, mixing and stirring to obtain a second mixture; (3) adding an antifouling agent and a stabilizer to the second mixture, mixing and stirring to obtain a third mixture, adding a solvent to the third mixture, mixing evenly, and filtering to obtain the underwater antifouling paint.

8. The method for preparing underwater antifouling paint according to claim 7, characterized in that: The mixing and stirring speed in step (1) is 1000-1500 r / min; The fineness of the third mixture in step (3) is less than 40 μm, and the viscosity of the third mixture after adding the solvent is 100-120 KU.

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